Method of forming aliphatic derivatives of aromatic compounds



UNITED STATES PATEN'll oFFIcE.

METHOD OF FORLIING ALIPHATIC DERIV TIVES OF'AROMATIC COMPOUNDS 7 George W. Seymour, Cumberland, Md., assignor to ,Celanese Corporation of America, a corporation of Delaware No Drawing. Application April 16, 1932,

Serial No. 605,791

8 Claims. (or zed-154') This invention relates to method of carrying yields are obtained by its use than when an= out chemical reactions and relates more partic- 'hydrous'aluminum chloride is used as condensing ularly to a new method or introducing aliphatic agent. a I groups into an aromatic nucleus by the use of a {In accordance with my invention I employ hynovel condensing agent; drated ferric chloride, that is, ferric chloride con- An object of my inventionjis to provide a new taining. water of crystallization, as a catalyst or condensing agent for the promotion of the recondensing agent for causing an aromatic comaction of an aliphatic halide with an aromatic pound to react with the halide of the aliphatic compound, particularly an aromatic compound group to be introduced into the aromatic nucleus.

19 containing a hydroxy group 'whereby the ali- Any suitable aromatic compound may be em-' phatic group is introduced into the nucleus o f'the, ployed as one of the reactants. Such aromatic aromatic compound. A further object of my in'-- compounds are preferably hydroxy nuclear sub- ,vention is touse hydrated ferric chloride as such stitution products of aromatic hydrocarbons such 1 condensing agent. Other objects of my inven-= as benzene, toluene, xylene, naphthalene or their tion will appear iromthe following detailed de-t nuclear substitution products wherein the nuclear scription. substituent group may be amino, chlorine or A method comm 'nly used forintroducing-alkyl other halogen, COOH, etc. This invention is of groups into aromatic compounds to form aralkyl particular interest in connection with the process compounds has been by the use or the Friedel and wherein phenols, such as phenol itself CsHsOH,

30 Crafts reaction, wherein anhydrous aluminum .cresols, naphthols or other hydroxy derivatives '85 chloride is used as a catalyst or condensing agent of aromatic compounds are to be employed as to cause an alkyl chloride to react with an the aromatic compound in the reaction. I have arom ti hydr c rb n wi h he l erati n of hyfound that better yields and smoother reactions drogen chloride. In'order to obtain proper reare obtainedwhen hydrated ferric chloride is 35 action and good yields it was necessary not only employed in reactions involving these phenols to employ absolutely anhydrous aluminum chlothan when anhydrous aluminum chloride or other ride and anhydrous reagents, but also it was anhydrous catalysts are employed. necessary to use freshly prepared or freshly Any suitable aliphatic halide may be used to sublimed aluminum chloride. This anhydrous react with the aromatic compound. This all- 30 aluminum chloride is relatively expensive and phatic halide may be halogenatedaliphatic'hydro-.88- difficult to store because otits great reactivity carbons such as methyl, ethyl, propyl, butyl or towards the moisture in the air. Moreover, in amyl chloride,bromide or iodide. However, other the case of reaction wlth'p'henols, this Friedel halogen compoundssuch as vinyl chloride, methand Crafts reaction gives very poor yields under ylenechloride, chloroform or acid chlorides, such 35 normal working conditions. a as acet-yl chloride, may be employed as reactants.

I have made the surprising discovery that con- In order further to illustrate my invention but trary to the known principles of the Friedel and without being limited thereto, the. following spe- Craits reaction, hydrated ferric chloridemay be cific examples are given: employed as condensing agent or catalyst in E w I 0 processes involving the reaction or an aliphatic xamp halide with an aromatic compound, particularly 1 molecular proportion 01 phenol and one moan aromatic compound containing hydroxy lecular proportion of tertiary butyl chloride and groups attached to the nucleus, whereby the halo- 0.2 molecular proportions of hydrated ferric chlogen combines with a hydrogen-o1 the aromatic ride, FC13.6H2O, are heated under reflux at 80 5 nucleus to form a. hydrogen halide, thus causing to 90 C. for 20 to 24 hours. The reaction mix- 109 the group originally attached to the halogen to ture is then poured into cold water whereupona be substituted in the aromatic compound. This large quantity of dark colored crystals are formed. discovery is contrary to the previously held the- These crystals are thoroughly washed and then ory that for reactions of this type, both the consteam distilled, after which they may be recrys- 50 -densing agent and the reactants should be tallized from acetic acid to form crystals of ter- 10s anhydrous. The use of hydrated ferric chloride tiary butyl phenol. for this purpose is or great commercial impor- Example H tance, since hydrated ferric chloride is very inexpensive, presents no dilllculty in storage, and The process of Example I is carried out except as in cases involving the reaction of a phenol better that tertiary amyl chloride is substituted for the m hill Example III 10 parts by weight of hydrated ferric chloride, FeChfiHzO are added to '50 parts by weight of phenol. The mass is heated to 100 C. and vinyl chloride is run in a slow stream through the same while stirring. After 60 parts by weight of vinyl chloride have been introduced, the reaction is In this manner tertiary stopped. Water is then added to the mixture and the vinyl phenol precipitated out.

The foregoing detailed description is given by way of illustration only, and many variations may be made therein without departing from the spirit of my invention.

Having described my invention what I claim and desire to secure by Letters Patent is:

1. Method of forming aliphatic derivatives of aromatic compounds comprising causing an aromatic compound containing replaceable nuclear hydrogen to react with an aliphatic halide in the presence of hydrated ferric chloride as catalyst or condensing agent, whereby the aliphatic group is introduced into the nucleus of the aromatic compound.

2. Method of forming alkyl derivatives of arcmatic compounds comprising causing an aromatic compound containing replaceable nuclear hydro gen to react with an alkyl halide in the presence of hydrated ferric chloride as catalyst or condensing agent, whereby the alkyl group is introduced into the nucleus of the aromatic compound.

3. Method of forming alkyl derivatives of aro- .densing agent, whereby the allzyl group is intrc= duced into the nucleus of the aromatic compound.

4. Method of forming aliphatic derivatives of phenol comprising causing a phenol to react with an aliphatic halide in the ferric chloride as catalyst or.condensing agent, whereby the aliphatic group is introduced into the nucleus of the phenol.

5. Method ofv forming alkyl derivatives of phenol comprising causing a phenol to react with an alkyl halide in the presence of hydrated ferric chloride as catalyst or condensing agent, whereby the alkyl group is introduced into the nucleus of the phenol.

6. Method of forming alkyl derivatives of phenol comprising causing a phenol to react with an alkyl chloride in the presence of hydrated ferric chloride as catalyst or condensing agent, whereby the alkyl group is introduced into the nucleus of. the phenol.

'7. Method of preparing butyl phenol compris ing causing phenol to react with butyl chloride in the presence of hydrated ferric chloride as catalyst or condensing agent.

8. Method of preparing amyl phenol comprising causing phenol to react with amyl chloride in the presence of hydrated ferric chloride as catalyst or condensing agent.

GEORGE w. ammonia.

presence of hydrated 

